CN105255416A - Room-temperature curing epoxy adhesive and preparation method thereof - Google Patents
Room-temperature curing epoxy adhesive and preparation method thereof Download PDFInfo
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- CN105255416A CN105255416A CN201510725122.1A CN201510725122A CN105255416A CN 105255416 A CN105255416 A CN 105255416A CN 201510725122 A CN201510725122 A CN 201510725122A CN 105255416 A CN105255416 A CN 105255416A
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Abstract
The invention provides a room-temperature curing epoxy adhesive and a preparation method thereof, which belongs to the technical field of adhesives. The room-temperature curing epoxy adhesive aims to solve the problems of poor mechanical properties and incapability of fast curing of an existing epoxy adhesive at room temperature. The adhesive comprises 100 parts of epoxy resin, 15 to 20 parts of aromatic amine curing agents, 2 to 10 parts of ionic liquid, 10 to 20 parts of thinners, 10 to 15 parts of plasticizers, 5 to 10 parts of fiber reinforced materials and 5 to 8 parts of filling agents, wherein the structural formula of the ionic liquid is shown in formula (I). The invention further provides a preparation method of the room-temperature curing epoxy adhesive. The preparation method has the advantages of simplicity and easiness in implementation, and the obtained adhesive can be cured at room temperature and has excellent mechanical properties.
Description
Technical field
The invention belongs to sizing agent technical field, be specifically related to a kind of room-temperature curing epoxy sizing agent and preparation method thereof.
Background technology
The liquid state that epoxy adhesive is made up of epoxy resin, solidifying agent, promotor, properties-correcting agent etc. or solid-state sizing agent.Because epoxy resin contains various polarity group and active very large epoxy group(ing), thus have very strong cohesive force with the various polarity material such as metal, glass, cement, timber, plastics, epoxy resin adhesive is widely used in industry and sphere of life with the over-all properties of its excellence.In the Application Areas of epoxy adhesive, the agent of self-vulcanizing gluing is because of its cheap process costs, and easy operation and spendable over-all properties become the first-selection in industrial circle.But heat-resisting group is few in the curable epoxide thing macromole of room temperature system, and self-vulcanizing temperature is low, cured article cross-linking density is little, therefore room-temperature curing epoxy system is difficult to meet usage requirement under the high temperature conditions, for many years people development can again can the epoxy adhesive of applied at elevated temperature in self-vulcanizing with great concentration always, to be satisfied with the application demand of the industry such as Aeronautics and Astronautics, electronics to high-performance epoxy resin.
At present, the applied defect of China's room-temperature curing epoxy tackiness agent is mainly manifested in: kind is few, and hot conditions Tensile strength, stripping strength, shearing resistance are poor, under room temperature can the kind such as fast setting very rare, quantity is few.Commercially available room temperature curing type tackiness agent only has tens at home.Poor performance, only has the room temperature shearing resistance of several trade mark epoxy glue such as J-135, J-153 to reach 30MPa, and most epoxy adhesive heat resisting temperatures is also only at 60 DEG C about-90 DEG C.In recent years, in self-vulcanizing, the research of applied at elevated temperature epoxy resin, achieve certain progress, but still cannot make a breakthrough.
Summary of the invention
The object of the invention is in order to solve existing epoxy adhesive poor mechanical property, at room temperature can not quick-setting problem, and provide a kind of room-temperature curing epoxy sizing agent and preparation method thereof.
First the present invention provides a kind of room-temperature curing epoxy sizing agent, according to weight parts, comprising:
The structural formula of described ionic liquid is as shown in formula I:
In formula I, R is BF
4, PF
6, AlCl
4, ZnCl
3or FeCl
4.
Preferably, the model of described epoxy resin is E-44, F-44, F-51, E-51 or TDE-85.
Preferably, described aromatic amine curing agent be selected from m-xylene diamine, mphenylenediamine or diaminodiphenyl-methane one or both.
Preferably, described thinner is glycidyl allyl ether, phenyl glycidyl ether or 2-ethyl hexyl glycidyl ether.
Preferably, described softening agent is o-phthalic acid dibutyl ester (DOP), polypropylene glycol diglycidyl ether or polythiol.
Preferably, described fiber reinforced material is boron fibre or glass fibre.
Preferably, described weighting agent is selected from Calucium Silicate powder, magnesium oxide, carbon black, aluminium hydroxide or calcium carbonate wherein one or both.
The present invention also provides a kind of preparation method of room-temperature curing epoxy sizing agent, comprising:
Epoxy resin is mixed with aromatic amine epoxy curing agent, stirs, then add ionic liquid, thinner, softening agent, fiber reinforced material and weighting agent, stir, remove bubble, obtain room-temperature curing epoxy sizing agent.
Beneficial effect of the present invention
First the present invention provides a kind of room-temperature curing epoxy sizing agent, this tackiness agent comprises ionic liquid, described ionic liquid is the functionalized ion liquid that a class has magnetic properties, it is made up of organic cation and inorganic or organic anion, the salt of the state that is in a liquid state under room temperature or near room temperature temperature, because of ionic liquid, to have liquid journey wide, steam forces down, dissolving power is strong, electrochemical stability advantages of higher and be widely used in electrochemistry, be separated, the fields such as catalysis, tackiness agent of the present invention is that the ionic liquid of different anions structure and aromatic amine curing agent are mixed and made into the composite solidifying agent of a series of room temperature according to different mass ratio, cured epoxy resin, can while room temperature fast-curing, the tensile strength of epoxy adhesive can be improved, shear, stripping strength and resistance toheat.
The present invention also provides a kind of preparation method of room-temperature curing epoxy sizing agent, and this preparation method is simple, and be easy to realize, the sizing agent prepared is namely curable at ambient temperature, and has excellent mechanical property.
Embodiment
First the present invention provides a kind of room-temperature curing epoxy sizing agent, according to weight parts, comprising: epoxy resin 100 parts, aromatic amine curing agent 15 ~ 20 parts, ionic liquid 2 ~ 10 parts, thinner 10 ~ 20 parts, 10 ~ 15 parts, softening agent, fiber reinforced material 5 ~ 10 parts, weighting agent 5 ~ 8 parts; Be preferably: epoxy resin 100 parts, aromatic amine curing agent 15 ~ 20 parts, ionic liquid 2 ~ 8 parts, thinner 10 ~ 15 parts, 10 ~ 15 parts, softening agent, fiber reinforced material 5 ~ 8 parts, weighting agent 6 ~ 7 parts;
The structural formula of described ionic liquid is as shown in formula I:
In formula I, R is BF
4, PF
6, AlCl
4, ZnCl
3or FeCl
4.
According to the present invention, adopt 1-hexyl-3-methyl imidazolium tetrafluoroborate ([C
6mim] BF
4), 1-hexyl-3-Methylimidazole hexafluorophosphate ([C
6mim] PF
6), 1-hexyl-3-Methylimidazole tri-chlorination zinc salt ([C
6mim] ZnCl
3), 1-hexyl-3-Methylimidazole aluminum tetrachloride salt ([C
6mim] AlCl
4), 1-hexyl-3-Methylimidazole titanium tetrachloride salt ([C
6mim] FeCl
4) as ionic liquid, tertiary amine is comprised in the molecular structure of described ionic liquid, quaternary ammonium salt structure, the characteristic group epoxy ring-opening solidification in epoxy resin structural can be caused and energy catalysis epoxide group, ionic liquid coordinates cured epoxy resin during with aromatic amine curing agent, good synergistic effect can be shown, effectively can overcome the conventional curing process of aromatic amine curing agent, necessary hot setting, just can the drawback of applied at elevated temperature, make it can at room temperature fast-curing, and cured article can be made to demonstrate excellent mechanical stretch intensity, shearing resistance, stripping strength and thermal characteristics.
According to the present invention, the model of described epoxy resin is preferably E-44, F-44, F-51, E-51 or TDE-85; Described aromatic amine curing agent be preferably selected from m-xylene diamine, mphenylenediamine or diaminodiphenyl-methane one or both; Described thinner is preferably glycidyl allyl ether, phenyl glycidyl ether or 2-ethyl hexyl glycidyl ether; Described softening agent is preferably o-phthalic acid dibutyl ester, polypropylene glycol diglycidyl ether or polythiol.Described fiber reinforced material is preferably boron fibre or glass fibre; Described weighting agent is preferably selected from Calucium Silicate powder, magnesium oxide, carbon black, aluminium hydroxide or calcium carbonate wherein one or both.
The present invention also provides a kind of preparation method of room-temperature curing epoxy sizing agent, comprising:
Epoxy resin is mixed with aromatic amine epoxy curing agent, stirs, then add ionic liquid, thinner, softening agent, fiber reinforced material and weighting agent, stir, remove bubble, obtain room-temperature curing epoxy sizing agent.
Being watered by above-mentioned tackiness agent casts from mould, places 30-40 DEG C of solidification 5min at ambient temperature, tests its mechanical property and thermal characteristics.
Below in conjunction with specific embodiment, the present invention will be further described in detail, and the raw material that embodiment relates to is commercially available.
Embodiment 1
By 100 parts of epoxy resin E-44s and 20 parts of mphenylenediamine mixing, stir, then the mixture (wherein Calucium Silicate powder, carbon black, aluminium hydroxide mass ratio are 3:1:2) of 5 parts of 1-hexyl-3-methyl imidazolium tetrafluoroborate, 10 parts of glycidyl allyl ethers, 15 parts of o-phthalic acid dibutyl esters, 5 parts of boron fibres, 5 parts of Calucium Silicate powder, carbon black, aluminium hydroxide is added, remove bubble, obtained sizing agent, sizing agent is watered cast from mould and reinforce, at being placed on 30-40 DEG C, solidify 5min.Concrete mechanical property is as shown in table 1.
Embodiment 2
By 100 parts of epoxy resin F-44 and 20 parts of m-xylene diamine mixing, stir, then 2 parts of 1-hexyl-3-Methylimidazole hexafluorophosphates, 12 parts of 2-ethyl hexyl glycidyl ethers, 15 parts of polypropylene glycol diglycidyl ethers, 8 parts of boron fibres, 8 parts of magnesium oxide are added, remove bubble, obtained sizing agent, sizing agent is watered cast from mould and reinforce, at being placed on 30-40 DEG C, solidify 5min.Concrete mechanical property is as shown in table 1.
Embodiment 3
100 parts of epoxy resin F-51 and 20 part mphenylenediamines are mixed with the mixture (mphenylenediamine and diaminodiphenyl-methane mass ratio are 3:2) of diaminodiphenyl-methane, stir, then 8 parts of 1-hexyl-3-Methylimidazole tri-chlorination zinc salts are added, 12 parts of phenyl glycidyl ethers, 10 parts of polypropylene glycol diglycidyl ethers and polythiol (wherein the mass ratio of polypropylene glycol diglycidyl ether and polythiol is 2:1), 5 parts of glass fibre, the mixture (calcium carbonate and aluminium hydroxide mass ratio are 2:3) of 6 parts of calcium carbonate and aluminium hydroxide, remove bubble, obtained sizing agent, sizing agent is watered cast from mould and reinforce, 5min is solidified at being placed on 30-40 DEG C.Concrete mechanical property is as shown in table 1.
Embodiment 4
By 100 parts of epoxy resin E-51 and 20 parts of m-xylene diamine mixing, stir, then 5 portions of 1-hexyl-3-Methylimidazole aluminum tetrachloride salt are added, the mixture (wherein glycidyl allyl ether and phenyl glycidyl ether mass ratio are 1:2) of 15 parts of glycidyl allyl ethers and phenyl glycidyl ether, 15 parts of polypropylene glycol diglycidyl ethers, 10 parts of glass fibre, 7 parts of calcium carbonate, mixture (the calcium carbonate of carbon black and aluminium hydroxide, carbon black, aluminium hydroxide mass ratio is 3:1:1), remove bubble, obtained sizing agent, sizing agent is watered cast from mould and reinforce, 5min is solidified at being placed on 30-40 DEG C.Concrete mechanical property is as shown in table 1.
Embodiment 5
By 100 parts of epoxy resin TDE-85 and 20 parts of diaminodiphenyl-methane mixing, stir, then 10 portions of 1-hexyl-3-Methylimidazole titanium tetrachloride salt, 10 parts of phenyl glycidyl ethers, 15 parts of polypropylene glycol diglycidyl ethers, 5 parts of glass fibre and 8 parts of aluminium hydroxides are added, remove bubble, obtained sizing agent, sizing agent is watered cast from mould and reinforce, at being placed on 30-40 DEG C, solidify 5min.Concrete mechanical property is as shown in table 1.
Comparative example 1
By 100 parts of epoxy resin E-44s and 20 parts of mphenylenediamine mixing, stir, then 10 parts of glycidyl allyl ethers and 2-ethyl hexyl glycidyl ether (wherein glycidyl allyl ether and 2-ethyl hexyl glycidyl ether mass ratio are 1:1) is added, 10 parts of polypropylene glycol diglycidyl ethers and polythiol be polypropylene glycol diglycidyl ether and polythiol mass ratio 1:2 wherein), 5 parts of boron fibres, 5 parts of calcium carbonate and aluminium hydroxide (wherein calcium carbonate and aluminium hydroxide mass ratio are 3:1), remove bubble, obtained sizing agent, sizing agent is watered cast from mould and reinforce, 6h is solidified at being placed on 120-150 DEG C.Concrete mechanical property is as shown in table 1.
Table 1
| Experiment parameter | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength (MPa) | 40 | 73 | 65 | 48 | 20 | 87 |
| Elongation at break (%) | 3 | 6 | 5 | 3 | 2 | 12 |
| Shearing resistance (MPa) | 19 | 18 | 20 | 21 | 20 | 25 |
| Stripping strength (MPa) | 31 | 32 | 33 | 32 | 30 | 36 |
| Thermal degradation temperature (DEG C) | 336 | 337 | 314 | 310 | 323 | 310 |
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a room-temperature curing epoxy sizing agent, is characterized in that, according to weight parts, comprising:
The structural formula of described ionic liquid is as shown in formula I:
In formula I, R is BF
4, PF
6, AlCl
4, ZnCl
3or FeCl
4.
2. a kind of room-temperature curing epoxy sizing agent according to claim 1, is characterized in that, the model of described epoxy resin is E-44, F-44, F-51, E-51 or TDE-85.
3. a kind of room-temperature curing epoxy sizing agent according to claim 1, is characterized in that, described aromatic amine curing agent be selected from m-xylene diamine, mphenylenediamine or diaminodiphenyl-methane one or both.
4. a kind of room-temperature curing epoxy sizing agent according to claim 1, is characterized in that, described thinner is glycidyl allyl ether, phenyl glycidyl ether or 2-ethyl hexyl glycidyl ether.
5. a kind of room-temperature curing epoxy sizing agent according to claim 1, is characterized in that, described softening agent is o-phthalic acid dibutyl ester, polypropylene glycol diglycidyl ether or polythiol.
6. a kind of room-temperature curing epoxy sizing agent according to claim 1, is characterized in that, described fiber reinforced material is boron fibre or glass fibre.
7. a kind of room-temperature curing epoxy sizing agent according to claim 1, is characterized in that, described weighting agent is selected from Calucium Silicate powder, magnesium oxide, carbon black, aluminium hydroxide or calcium carbonate wherein one or both.
8. the preparation method of a kind of room-temperature curing epoxy sizing agent of claim 1-7 described in any one, is characterized in that, comprising:
Epoxy resin is mixed with aromatic amine epoxy curing agent, stirs, then add ionic liquid, thinner, softening agent, fiber reinforced material and weighting agent, stir, remove bubble, obtain room-temperature curing epoxy sizing agent.
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|---|---|---|---|
| CN201510725122.1A CN105255416A (en) | 2015-10-29 | 2015-10-29 | Room-temperature curing epoxy adhesive and preparation method thereof |
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|---|---|---|---|
| CN201510725122.1A CN105255416A (en) | 2015-10-29 | 2015-10-29 | Room-temperature curing epoxy adhesive and preparation method thereof |
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Cited By (5)
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| CN105968726A (en) * | 2016-07-12 | 2016-09-28 | 四川大学 | Epoxy resin in double-crosslinked-network structure and preparation method thereof |
| CN107151544A (en) * | 2017-07-12 | 2017-09-12 | 苏州润德新材料有限公司 | A kind of bonded adhesives for crystalline silicon rod |
| CN107587693A (en) * | 2017-08-16 | 2018-01-16 | 浙江林境新材料科技有限公司 | A kind of floor |
| CN111423835A (en) * | 2020-04-15 | 2020-07-17 | 中国科学院过程工程研究所 | COB electronic packaging adhesive and preparation method thereof |
| CN111808566A (en) * | 2020-07-20 | 2020-10-23 | 郯城博化化工科技有限公司 | Epoxy resin adhesive for electronic device and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968726A (en) * | 2016-07-12 | 2016-09-28 | 四川大学 | Epoxy resin in double-crosslinked-network structure and preparation method thereof |
| CN105968726B (en) * | 2016-07-12 | 2017-11-28 | 四川大学 | Epoxy resin with double cross-linked network structures and preparation method thereof |
| CN107151544A (en) * | 2017-07-12 | 2017-09-12 | 苏州润德新材料有限公司 | A kind of bonded adhesives for crystalline silicon rod |
| CN107587693A (en) * | 2017-08-16 | 2018-01-16 | 浙江林境新材料科技有限公司 | A kind of floor |
| CN111423835A (en) * | 2020-04-15 | 2020-07-17 | 中国科学院过程工程研究所 | COB electronic packaging adhesive and preparation method thereof |
| CN111423835B (en) * | 2020-04-15 | 2021-08-17 | 中国科学院过程工程研究所 | COB electronic packaging adhesive and preparation method thereof |
| CN111808566A (en) * | 2020-07-20 | 2020-10-23 | 郯城博化化工科技有限公司 | Epoxy resin adhesive for electronic device and preparation method thereof |
| CN111808566B (en) * | 2020-07-20 | 2022-05-31 | 郯城博化化工科技有限公司 | Epoxy resin adhesive for electronic device and preparation method thereof |
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